CN105713316A - Transparent phenol-free pasty heat stabilizer and preparing method thereof - Google Patents
Transparent phenol-free pasty heat stabilizer and preparing method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the technical field of heat stabilizers, in particular to a transparent phenol-free environment-friendly pasty heat stabilizer and a preparing method thereof. The pasty heat stabilizer is prepared from, by weight, 2-10 parts of calcium salt main stabilizer, 10-25 parts of zinc salt main stabilizer, 12-25 parts of hydrotalcite, 3-12 parts of beta-diketone, 3-10 parts of antioxidant, 8-20 parts of chelation compound, 5-15 parts of viscosity reducer and 32-55 parts of epoxy compound. The pasty heat stabilizer completely meets the phenol-free environment-friendly requirement, transparency and later-stage heat resistance are high, and the prepared product is free of red stain for a long time, high in dispersion mobility and free of lamination; besides, processing range is wide, and the pasty heat stabilizer is suitable for flexible, semi-rigid and high-transparency PVC extrusion and injection molding, and paste resin plastic processing.
Description
Technical field
The present invention relates to heat stabilizer technical field, be specifically related to a kind of transparent paste shape heat stabilizer of environmental protection without phenol and
Preparation method.
Background technology
PVC plastic processing is main by the agitated mixing of material, high temperature such as polyvinyl chloride resin base material, plasticiser, heat stabilizers
The operations such as melted, plasticizing forming, finally prepare required product.Wherein, the effect of heat stabilizer is very important.
PVC plastic heat stabilizer kind is more, has heavy metal lead, cadmium type thermal stabilizing agent, Ca-Zn composite heat stabilizer (liquid
Shape/powdery/paste shape), organo-tin het stabilizer and organic group heat stabilizer etc..Although lead, cadmium type thermal stabilizing agent are functional,
Along with increasingly stricter to environmental requirement both at home and abroad, application is limited significantly.Wherein, organic group heat stabilizer is (such as urine
Miazines), it is only applicable to hard PVC processing, the range of work is narrow.And for organo-tin het stabilizer, if only from transparent
Degree and heat ageing index are assessed, its excellent performance；But can the unpleasant penetrating odor of long-term existence, to environment and
Health of human body causes potential hazard.
Moreover, it is well known that three kinds of industrial chemicals, such as bisphenol-A, nonyl phenol and phenol, industrial application value is relatively
High.Wherein, bisphenol-A (Bisphenol A is called for short BPA) is commonly used for polycarbonate synthesis plastics and epoxy resin etc..The whole world
27,000,000 tons of plastics containing BPA of annual production.BPA is ubiquitous, mineral water bottle, medical apparatus and instruments to and packaging material for food
There is its figure.But BPA is known endocrine disruptors (Environmental Hormone), can cause endocrine disturbance, threaten
Fetus and the health of child, the EU criteria identification feeding bottle containing BPA can induce sexual precosity.And cancer and metabolic disturbance are led
The obesity caused is recognized as relevant with this.
Wherein, nonyl phenol (Nonyl Phenol is called for short NP) is a kind of important fine chemical material and centre equally
Body, mainly for the production of surfactant, be also used for antioxidant, textile auxiliary, lube oil additive, farm chemical emulgent,
The fields such as modifier, resin and rubber stabilizer.NP has strong lipotropy, is not easily decomposed in the environment, again because of it
Chemical constitution is similar with the estrogen of animal and the mankind, once enters animal and the normal life of body interior meeting disturbance endocrine
Reason effect.
Studying discovery recently, NP can reduce the metabolism to androgen of the human body prostate, to the reproductive performance of male and
Health status can cause serious threat really.Owing to NP belongs to, biology is had dysgenic Environmental Hormone, united nations environment
Programme division (UNEP) is listed in " toxic persistent material inventory ".P-nonyl phenol belongs to the one of alicyclic phenol derivatives, many
P-nonyl phenol is added in polystyrene and polrvinyl chloride in order to increase stablizing of plastics by number factory as a kind of antioxidant
Property.Germany's " ecological test " magazine discloses the up-to-date examining report to 30 kinds of toys recently, is found that nonyl in 15 kinds of toys
Base phenol.Now state of European Union (especially Germany) has carried out control to following four kinds of nonyl phenols: nonyl phenol (NP), nonyl benzene
Phenol ethoxy compound (NPEO), octyl phenol (OP) and octyl phenol ethoxy compound (OPEO).
It addition, phenol (Phenol) is a kind of common chemicals, be produce some resin, antibacterial, preservative and
The important source material of medicine (such as aspirin).Low Concentration Phenol can make albuminous degeneration, and high concentration phenol can make albumen precipitation.And benzene
Phenol has strong corrosiveness to skin, mucosa, it is possible to suppression central nervous system or infringement Liver and kidney function.
In July, 2013, European Union new environmental regulation EN71-PART3 puts into effect, it is desirable to plastic limits including stannum (Sn)
Heavy metal 19 (European Union RoSH 2.0 limit require increase by 10), toxic substance BPA content should be less than 1ppm；At toy
Field, EN71 environmental regulation requires that toxic substance Phenol content should be less than 5ppm, NP content and should be less than 50ppm.Additionally,
PVC product containing phenol exposes in atmosphere, easily becomes 1,4-benzoquinone (C because of oxidation of phenol6H4O2) to make PVC product present pink
Form and aspect, cause the quality of goods to be greatly reduced.Therefore, limit multinomial important indicator in conjunction with heavy metal 19 and phenol content, have
Machine stannum stabilizer and liquid composite stabilizing agent are inapplicable in fields such as toys.
At present, the Powdery calcium-zinc complex heat stabilizer of transparent PVC processing purposes it is commonly used on the market, such as Dongguan Shang Nuo
Company CZ-1059 series, if sky, Dongguan company RT-600 is serial, Germany's Xiong Pai company MC-9875KA series, Japan's marshy land strain formula
Commercial firm A200P/A400P series, the OW-5200 series of Sakai company of Japan, Japan's rising sun electrification company RUP-177 series etc.；On
Though it is heat-resisting well to state heat stabilizer, but range of work great majority are recommended to be applicable to soft pvc plastic, such as flexible plastics such as electric wires
Processing, and in semi-rigid (plasticizer loading≤30phr, shore hardness 90A-100A) plastic processes, because powder body is stable
Agent viscosity is relatively big, and dispersion flows is poor, causes melt to be heated in die cavity inequality, and the easy xanthochromia of goods, transparency is also by shadow
Ring.
Both at home and abroad scientific research institution's research worker is for the research of paste shape stabilizer and application, also never interrupts.Shen
Please number be 201010582178.3 Chinese invention patent disclose a kind of pasty state calcium-zinc composite stabilizing agent and preparation method thereof, thoroughly
Bright property is preferable, and its stabilizer prepared have employed phenoxy group structure (PhO-) chelating agen (nontoxic phosphite ester), commercially available such
Material is generally used for the goods that environmental requirement is the highest, its bisphenol-A and phenol content typically in 6000-120000ppm scope, because of
This can not be limited by the phenol content of the new environmental regulation of European Union.And by use the method prepare PVC product, easy because of
The oxidation of phenol of residual becomes 1,4-benzoquinone (C6H4O2), cause the goods later stage slowly to present pink form and aspect, have a strong impact on product property.
Additionally, Related product also has Germany Galata company pasty state stabilizer MARK-CZ113, it is recommended that for the antifog preservative film of PVC transparent
Process with sticking with paste；Ai Ke AKCROS company of Britain pasty state stabilizer ZX-9050/9011, it is recommended that for medical sanitary field.
It is to say, presently disclosed pasty state calcium-zinc composite stabilizing agent and semi-fluid solid-liquid phase complex stabilizer, great majority
Only focusing on the transparency or the thermostability of plastics, combination property has open defect, and the application range of work is narrow；If long-time storage,
Solid-liquid phase lamination easily occurs；Meanwhile, it substantially ignores the main idea of timely environmental protection, it is impossible to newly want with world's environmental protection
Seek common ground step.
Although additionally, prior art has the performance using chelate compound to improve heat stabilizer, but its chelating added
Compound cannot meet environmental requirement at all.Generally speaking, traditional chelate compound mainly has two classes, and one type is sequestration
Compound is mainly nontoxic phosphorous acid esters, such as phosphorous acid-4,4-bis-different fork bis-phenol carbon Arrcostab (Mark-1500/N), phosphorous acid
Triphenylmethyl methacrylate (TPP), diisooctyl phenyl phosphite (PDOP), the different certain herbaceous plants with big flowers ester of phosphorous acid one benzene two (PDDP), phosphorous acid diphenyl are different
Certain herbaceous plants with big flowers esters (DPDP) etc., owing to it contains phenoxy group (ArO-) group and phenoxy group structural derivative, and use C12～C14 synthesis
Alcohol, not only alcohol is highly seasoned, and later stage anti-aging effect is general, facile hydrolysis produces free phenol and phenol, belongs to poisonous and low drugs, no
Can be used for articles for babies, medical and plastic toys.Another kind of chelate compound, such as distearyl pentaerythritol phosphite
(Weston 618), although available phosphorus content is high, hydroperoxide decomposition ability is strong, has effectively restrained polymer autoxidation anti-
Should, delay the degradation with aging speed of material, but, use triphenyl phosphite to be raw material because of it equally, product has phenol residual
Remaining, limit the application at food packaging applications of such material.
In view of this, a kind of range of work of necessary research and development is wide, it is adaptable to soft, semi-rigid PVC plastic processing, dispersion
Good fluidity, transparency are high, the later stage is heat-resist, do not produce red change, and be entirely free of nonyl phenol (NonylPhenol, NP),
Bisphenol-A (Bisphenol A, BPA), the environmentally-friendly transparent heat stabilizer of phenol (Phenol).
Summary of the invention
It is an object of the invention to: for the deficiencies in the prior art, it is provided that a kind of transparent shape heat stabilizer of paste without phenol and
Its preparation method.The transparent shape heat stabilizer excellent clarity of paste without phenol provided by the present invention, later stage heat resistance are good, gained
Goods have and do not occur for a long time that red change, dispersion flows be good, advantage without lamination generation；And its production cost is low, complete
Entirely meet the environmental requirement without phenol of new legislation, there is higher using value；Additionally, transparent paste without phenol provided by the present invention
The shape heat stabilizer application range of work is wide, it is adaptable to soft, the extrusion of semi-rigid high transparency PVC plastic, is molded and sticks with paste resin plastic
Material processing technique.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of transparent shape heat stabilizer of paste without phenol, including following composition by weight:
Wherein, described calcium salt main stabilizer is the mixing of one or two kinds of arbitrary proportion of calcium stearate and calcium laurate
Thing；Described zinc salt main stabilizer is the mixture of the one or two kinds of arbitrary proportion of zinc stearate and Dodecanoic acid, zinc salt；
Described chelate compound is the PAPE of targeting carbon-chain structure (carbon number is C7～C10 and C16～C18),
The PAPE of described targeting carbon-chain structure is that diphosphorous acid two different certain herbaceous plants with big flowers ester group pentaerythritol ester is (by tetramethylolmethane, phosphorous
Prepared by triethylenetetraminehexaacetic acid ester and different certain herbaceous plants with big flowers alcohol 1:2.0:2.0 in molar ratio), diphosphorous acid two (benzyl alcohol) pentaerythritol ester is (by Ji Wusi
Prepared by alcohol, NSC 5284 and benzyl alcohol 1:2.0:2.0 in molar ratio), diphosphorous acid distearyl pentaerythritol ester is (by season
Prepared by penta tetrol, NSC 5284 and octadecanol 1:2.05:2.05 in molar ratio), double (18-amine. base phosphorous acid) Ji Wusi
Alcohol ester (being prepared by tetramethylolmethane, NSC 5284 and 18-amine. 1:2.10:2.10 in molar ratio), diphosphorous acid two (16
Alcohol) one or of pentaerythritol ester (by 1: 2.08: 2 preparation in molar ratio of tetramethylolmethane, NSC 5284 and hexadecanol)
The mixture mixed in any proportion more than kind.Wherein, diphosphorous acid two different certain herbaceous plants with big flowers ester group pentaerythritol ester and diphosphorous acid two (benzene
Methanol) pentaerythritol ester is the PAPE of C7～C10 chain；Diphosphorous acid distearyl pentaerythritol ester, double (18-amine.
Base phosphorous acid) pentaerythritol ester and PAPE that diphosphorous acid two (hexadecanol) pentaerythritol ester is C16～C18 chain.
Present invention utilizes such chelate compound and there is high content of phosphorus (11%-12.2%), compensate for heat-resisting deficiency
Defect；Wherein C16～C18 PAPE chelate compound, have employed food stage C16～C18 natural coconut alcohol is raw material,
The most tasteless, stablizing effect is more preferably；And the polyol ester of targeting carbon-chain structure (C7～C10 and C16～C18) all uses phosphorous
Triethylenetetraminehexaacetic acid ester, Phosphorous chloride. do not contain phenol and free phenol as primary response raw material, product so that use the product of this heat stabilizer
Comply fully with without phenol requirement.
Wherein, tetramethylolmethane often with zinc-base stabilizer with there being cooperative effect, it can replace allyl chloride makes PVC steady
Fixed, but its higher fusing point 262 DEG C, it is impossible to melted under the conditions of PVC machine-shaping temperature (120-210 DEG C), it is thoroughly simultaneously
Bright PVC adds and is also used by restriction man-hour.And tetramethylolmethane is because of containing polyhydroxy structure, sterically hindered relatively big, with the PVC compatibility
Difference, has great bloom risk.The chelate compound that the present invention uses is the bisphosphite that pentaerythritol ester is derivative, effectively
Phosphorus content is high, decomposition of hydrogen peroxide ability is strong, heat-resist；Such chelate compound simultaneously, solid-state fusion range is 42～60
DEG C, good with the PVC compatibility, do not separate out.
Additionally, the chelate compound of targeting carbon-chain structure that the present invention chooses, such as double (18-amine. base phosphorous acid) Ji Wusi
Alcohol ester, owing to its intramolecular contains tetramethylolmethane, hypophosphorous acid root and fatty amine, the free radical capture effect of primary antioxidant, auxiliary
The hydroperoxide decomposition effect of aid anti-oxidants and chelation of metal ion are compounded in an intramolecular, are a kind of intramoleculars
Complex type antioxidant and heat stabilizer；When it is with metal ion-chelant, in addition to the oxygen atom of phosphorous acid participates in chelating, the nitrogen in amine
Atom also assists in chelating, so that chelate is more stable, therefore antioxygen property and stability are all remarkably reinforced.
Described thinner is 2,2,4-trimethyl-1,3-pentanediol double isobutyrate, dibenzoic diglycol laurate, 4,5-ring
Oxygen hexane-1,2-dioctyl phthalate dioctyl ester, one or more mixture mixed in any proportion of white oil.Wherein, white oil
With straight run oil, be hydrocracked fraction oil or low-sulfur straight run boat coal as raw material, make through deep hydrofinishing aftercut.Existing
There are the pasty state under technical conditions and semi-fluid solid-liquid phase composite thermal stabilizer product, or because viscosity is relatively big, dispersion flows is not
Good；Or because viscosity is less, the short time there will be solid-liquid phase layering, has quality risk of instability, is not suitable for long-time storage.This
Invention uses thinner to get involved solid-liquid phase system, and the different groups at its molecule two ends have affinity to biphase respectively, make biphase
All regarded as the composition of this phase, i.e. molecules align between the two phases, make biphase surface be equivalent to incorporate intramolecule, thus
Reduce surface free energy.It is to say, due to the biphase component all being regarded as this phase, desalinated two in this way
The interface of individual phase so that surface tension and surface free energy are minimized, thus reduce the viscosity of solid-liquid phase system so that
Dispersion flows is good, and keeps stablizing of viscosity, it is suppressed that solid-liquid phase lamination.Additionally, the 4 of present invention employing, 5-epoxy
Hexane-1,2-dioctyl phthalate dioctyl ester, because its molecular structure is special epoxy construction, resin deep processing is had certain resistance to by it
Thermal compensation performance.
Described epoxide is that epoxy soybean oil, unsaturated fatty acid epoxy-ester, epoxyoleic acid butyl ester, Epoxy oil are misery
Ester, one or more mixture mixed in any proportion of epoxyoleic acid ester in the last of the ten Heavenly stems.Wherein, described epoxide and
The performance indications scope of its derivant: oxirane oxygen content 4.5-6.6%, iodine number≤6.0.
Described brucite is binary magnesium-aluminum hydrotalcite, Zn-Al binary hydrotalcite and the one or of magnalium zinc ternary hydrotalcite
The mixture mixed in any proportion more than kind；MgO/Al in described binary magnesium-aluminum hydrotalcite2O3Concentration than for (4.0～
4.5): 1, ZnO/Al in described Zn-Al binary hydrotalcite2O3Concentration than for (0.5～1.0): 1, described magnalium zinc ternary neatly
MgO/ZnO/Al in stone2O3Concentration than for (1.0～2.5): (0.25～0.5): 1.
Described beta-diketon is dibenzoyl methane, stearoyl benzoyl methane, isobutyl phenyl ketone formyl methane, Xin Benjiaxianjia
Alkane, one or more mixture mixed in any proportion of three (2-ethoxy) chlorinated isocyanurates.Beta-diketon and calcium zinc
Main stabilizer is collaborative to play a role, and can significantly improve the heat stability of PVC, and have enhancing and toughness reinforcing effect to PVC.
Described antioxidant is hindered phenol anti-oxidants, and described hindered phenol anti-oxidants is β-(3,5-di-t-butyl-4-
Hydroxy phenyl) propanoic acid positive octadecanol ester and the one of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester
Plant or the mixture of two kinds of arbitrary proportions.Hindered phenol anti-oxidants and chelate compound synergism, efficiently solve system
Product technique initial coloration (transparency) and the problem in later stage aging (thermostability).
Preferably, a kind of transparent shape heat stabilizer of paste without phenol, including following composition by weight:
Preferably, a kind of transparent shape heat stabilizer of paste without phenol, including following composition by weight:
Preferably, a kind of transparent shape heat stabilizer of paste without phenol, including following composition by weight:
The preparation method of the described transparent shape heat stabilizer of paste without phenol comprises the following steps:
Step one, according to above-mentioned formula metering, epoxide, thinner, chelate compound are rendered to explosion-proof successively
Mixed at high speed reactor, mixes 5-8min under the conditions of 55-62 DEG C；
Step 2, throw in the calcium salt main stabilizer of above-mentioned formula metering, zinc salt main stabilizer, brucite the most in order,
15-20min is mixed under the conditions of 55-62 DEG C；
Step 3, finally beta-diketon and antioxidant are rendered to high speed reactor, under the conditions of 55-62 DEG C, mix 25-
After 35min, then standing froth breaking 10-15min, cooling material, to 35 ± 2 DEG C, i.e. prepares the transparent shape heat stabilizer of paste without phenol.
Preferably, the temperature of described step one and step 2 controls respectively at 58-62 DEG C.
Preferably, the rotating speed of the mixed at high speed reactor of described step one and step 2 is respectively 600-1200r/min.
The present invention compared with prior art, has the beneficial effects that:
1) a kind of transparent shape heat stabilizer of paste without phenol of the present invention, including following composition by weight: calcium salt master is steady
Determine agent 2-10 part, zinc salt main stabilizer 10-25 part, brucite 12-25 part, beta-diketon 3-12 part, antioxidant 3-10 part is sequestration
Compound 8-20 part, thinner 5-15 part, epoxide 32-55 part, owing to selecting the targeting carbon-chain structure without the synthesis of phenol technique
Polyol ester chelate compound, plastic processes does not has phenol and phenol derivatives to occur so that use this heat stabilizer
Product comply fully with without phenol requirement；And make use of such material to have high content of phosphorus, and compensate for the defect of heat-resisting deficiency, permissible
Making the PVC product resting period be greatly prolonged, goods do not redden；Make PVC product transparency height, fine heat-resisting performance simultaneously；
2) chelate compound that the present invention uses is the bisphosphite that pentaerythritol ester is derivative, itself and zinc-base stabilizer
And with there being cooperative effect, such chelate compound available phosphorus content is high, decomposition of hydrogen peroxide ability is strong, heat-resist；Should simultaneously
Class chelate compound, solid-state fusion range is at 42～60 DEG C, good with the PVC compatibility, does not separates out；
3) present invention uses thinner to get involved solid-liquid phase system, and the different groups at its molecule two ends have biphase respectively
Affinity, makes the biphase composition all being regarded as this phase, has desalinated the interface of two phases in this way so that surface tension
It is minimized with surface free energy, thus reduces the viscosity of solid-liquid phase system so that it is dispersion flows is good, and keeps viscosity
Stablize, it is suppressed that solid-liquid phase lamination；
4) preparation method of the present invention is simple, and production cost is low, has higher market using value.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention and beneficial effect thereof are described in further detail, but, the present invention
Detailed description of the invention be not limited thereto.
Embodiment 1
Weigh 4kg diphosphorous acid distearyl pentaerythritol ester, 8kg diphosphorous acid two different certain herbaceous plants with big flowers ester group pentaerythritol ester, 7kg
2,2,4-trimethyl-1,3-pentanediol double isobutyrate, 40kg epoxy soybean oil, render to explosion-proof mixed at high speed reactor successively
In, mixing rotating speed is set to 600r/min, mixes 7min under the conditions of 58 DEG C；Throw in 2kg calcium stearate, 12kg the most in order hard
Fat acid zinc, 18kg binary magnesium-aluminum hydrotalcite, be promoted to 800r/min by mixing rotating speed simultaneously, mixes 15min under the conditions of 58 DEG C；
Last toward hybrid reactor input 5kg dibenzoyl methane, 4kg β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive 18
Carbon alcohol ester, mixes 30min under same rotational speed and temperature conditions, stands froth breaking 15min under the conditions of 58 DEG C, and cooling material is to 35
DEG C, the transparent shape heat stabilizer of paste without phenol of the present invention can be obtained.
Embodiment 2
Weigh double (the 18-amine. base phosphorous acid) pentaerythritol ester of 6kg, 8kg diphosphorous acid two different certain herbaceous plants with big flowers ester group pentaerythritol ester,
The 2 of 8kg, 2,4-trimethyl-1,3-pentanediol double isobutyrate, 37kg unsaturated fatty acid epoxy-ester, render to explosion-proof successively
In mixed at high speed reactor, mixing rotating speed is set to 600r/min, mixes 8min under the conditions of 58 DEG C；Throw in 10kg the most in order
Calcium stearate, 12kg Dodecanoic acid, zinc salt, 20kg magnalium zinc ternary hydrotalcite, be promoted to 800r/min by mixing rotating speed, 58 simultaneously
20min is mixed under the conditions of DEG C；Last toward hybrid reactor input 4kg stearoyl benzoyl methane, 3kg tetra-[β-(3,5-bis-tertiary fourths
Base-4-hydroxy phenyl) propanoic acid] pentaerythritol ester, under same rotational speed and temperature conditions, mix 35min, quiet under the conditions of 58 DEG C
Putting froth breaking 10min, cooling material, to 35 DEG C, can obtain the transparent shape heat stabilizer of paste without phenol of the present invention.
Embodiment 3
Weigh 5kg diphosphorous acid two (hexadecanol) pentaerythritol ester, 8kg diphosphorous acid two different certain herbaceous plants with big flowers ester group pentaerythritol ester,
11kg dibenzoic diglycol laurate, 32kg epoxyoleic acid butyl ester, render in explosion-proof mixed at high speed reactor successively, mixes rotating speed
It is set to 600r/min, under the conditions of 58 DEG C, mixes 8min；Throw in 4kg calcium stearate, 9kg zinc stearate, the 4kg month the most in order
Cinnamic acid zinc, 20kg binary magnesium-aluminum hydrotalcite, be promoted to 800r/min by mixing rotating speed simultaneously, mixes 20min under the conditions of 58 DEG C；
Last toward hybrid reactor input 3kg isobutyl phenyl ketone formyl methane, 2kg stearoyl benzoyl methane, 4kg β-(tertiary fourth of 3,5-bis-
Base-4-hydroxy phenyl) propanoic acid positive octadecanol ester, under same rotational speed and temperature conditions, mix 30min, quiet under the conditions of 58 DEG C
Putting froth breaking 10min, cooling material, to 35 DEG C, can obtain the transparent shape heat stabilizer of paste without phenol of the present invention.
Embodiment 4
Weigh 13kg diphosphorous acid two (benzyl alcohol) pentaerythritol ester, 8kg white oil, 38kg epoxyoleic acid monooctyl ester, throw successively
Being put in explosion-proof mixed at high speed reactor, mixing rotating speed is set to 600r/min, mixes 5min under the conditions of 60 DEG C；The most in order
Throw in 3kg lauric acid, 10kg zinc stearate, 15kg magnalium zinc ternary hydrotalcite, 2kg Zn-Al binary hydrotalcite, simultaneously will mixing
Rotating speed is promoted to 800r/min, mixes 15min under the conditions of 60 DEG C；Last past hybrid reactor input 5kg pungent benzoyl methane,
6kg β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, mixes under same rotational speed and temperature conditions
25min, stands froth breaking 10min under the conditions of 60 DEG C, and cooling material, to 35 DEG C, can obtain transparent paste without phenol of the present invention
Shape heat stabilizer.
The preparation method of embodiment 5-15 is same as in Example 1, repeats no more, and different compositions and content see table 1:
Table 1 embodiment composition table
In order to beneficial effects of the present invention more can be embodied, use following comparative example 1～4.Wherein, comparative example 1 is that liquid is saturating
Bright calcium zinc stabilizer, comparative example 2 is the transparent calcium zinc stabilizer of powder body, and comparative example 3 is existing pasty state calcium zinc stabilizer, comparative example
4 is methyl tin heat stabilizer, and composition and the content of each comparative example are shown in Table 2.
Table 2 comparative example composition table
Respectively embodiment 1-15 and comparative example 1-4 being carried out experiment test, test result is shown in Table 3 and table 4.
Table 3 heat stability, light transmittance, complexion changed test result table
Being shown by the test result of table 3, relative to existing heat stabilizer, the present invention transparent paste without phenol shape is thermally-stabilised
Agent, not only heat resistance is excellent, transparency is high, and color-change resistant performance is good.
Table 4: phenol content measuring and other performance data test result table
From the test result of table 4, relative to existing heat stabilizer, the transparent shape of paste without phenol of the present invention is thermally-stabilised
Agent complies fully with environmental protection without phenol requirement, and resulting product has that longer-term storage does not reddens, dispersion flows is good, produce without lamination
Raw advantage.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula changes and revises.Therefore, the invention is not limited in above-mentioned specific embodiment, every those skilled in the art are at this
Any conspicuously improved, replacement done on the basis of invention or modification belong to protection scope of the present invention.Additionally,
Although this specification employing some specific terms, but these terms is merely for convenience of description, not to structure of the present invention
Become any restriction.
Claims (10)
1. the transparent shape heat stabilizer of paste without phenol, it is characterised in that include following composition by weight:
Calcium salt main stabilizer 2-10 part
Zinc salt main stabilizer 10-25 part
Brucite 12-25 part
Beta-diketon 3-12 part
Antioxidant 3-10 part
Chelate compound 8-20 part
Thinner 5-15 part
Epoxide 32-55 part；
Wherein, described calcium salt main stabilizer is the mixture of one or two kinds of arbitrary proportion of calcium stearate and calcium laurate；
Described zinc salt main stabilizer is the mixture of the one or two kinds of arbitrary proportion of zinc stearate and Dodecanoic acid, zinc salt；
Described chelate compound is the PAPE of targeting carbon-chain structure, the PAPE of described targeting carbon-chain structure
For diphosphorous acid two different certain herbaceous plants with big flowers ester group pentaerythritol ester, diphosphorous acid two (benzyl alcohol) pentaerythritol ester, diphosphorous acid distearyl
Pentaerythritol ester, double (18-amine. base phosphorous acid) pentaerythritol ester, the one of diphosphorous acid two (hexadecanol) pentaerythritol ester or
More than one mixture mixed in any proportion.
One the most according to claim 1 transparent paste without phenol shape heat stabilizer, it is characterised in that: described thinner is 2,
The double isobutyrate of 2,4-trimethyl-1,3-pentanediol, dibenzoic diglycol laurate, 4,5-oxepane-1,2-dioctyl phthalate two are pungent
Ester, one or more mixture mixed in any proportion of white oil.
One the most according to claim 1 transparent paste without phenol shape heat stabilizer, it is characterised in that: described epoxy compound
Thing be epoxy soybean oil, unsaturated fatty acid epoxy-ester, epoxyoleic acid butyl ester, epoxyoleic acid monooctyl ester, the one of epoxyoleic acid ester in the last of the ten Heavenly stems
Plant or more than one mixture mixed in any proportion.
One the most according to claim 1 transparent paste without phenol shape heat stabilizer, it is characterised in that:
Wherein, described brucite be binary magnesium-aluminum hydrotalcite, Zn-Al binary hydrotalcite and the one of magnalium zinc ternary hydrotalcite or
More than one mixture mixed in any proportion；
Described beta-diketon be dibenzoyl methane, stearoyl benzoyl methane, isobutyl phenyl ketone formyl methane, pungent benzoyl methane,
One or more mixture mixed in any proportion of three (2-ethoxy) chlorinated isocyanurates；
Described antioxidant is hindered phenol anti-oxidants, and described hindered phenol anti-oxidants is β-(3,5-di-t-butyl-4-hydroxyls
Phenyl) propanoic acid positive octadecanol ester and the one of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester or
The mixture of two kinds of arbitrary proportions.
One the most according to claim 4 transparent paste without phenol shape heat stabilizer, it is characterised in that:
MgO/Al in described binary magnesium-aluminum hydrotalcite2O3Concentration than for (4.0 ~ 4.5): 1, in described Zn-Al binary hydrotalcite
ZnO/Al2O3Concentration than for (0.5 ~ 1.0): 1, MgO/ZnO/Al in described magnalium zinc ternary hydrotalcite2O3Concentration ratio be
(1.0 ~ 2.5): (0.25 ~ 0.5): 1.
One the most according to claim 1 transparent paste without phenol shape heat stabilizer, it is characterised in that include following by weight
The composition of part meter:
Calcium salt main stabilizer 2-8 part
Zinc salt main stabilizer 10-20 part
Brucite 10-20 part
Beta-diketon 3-10 part
Antioxidant 5-10 part
Chelate compound 8-18 part
Thinner 8-15 part
Epoxide 35-45 part.
One the most according to claim 6 transparent paste without phenol shape heat stabilizer, it is characterised in that include following by weight
The composition of part meter:
Calcium salt main stabilizer 3-5 part
Zinc salt main stabilizer 10-15 part
Brucite 15-20 part
Beta-diketon 3-8 part
Antioxidant 5-8 part
Chelate compound 12-18 part
Thinner 8-12 part
Epoxide 35-40 part.
One the most according to claim 7 transparent paste without phenol shape heat stabilizer, it is characterised in that include following by weight
The composition of part meter:
Calcium salt main stabilizer 3 parts
Zinc salt main stabilizer 10 parts
Brucite 17 parts
Beta-diketon 5 parts
6 parts of antioxidant
Chelate compound 13 parts
Thinner 8 parts
Epoxide 38 parts.
9. according to one transparent paste without the phenol shape heat stabilizer described in any one of claim 1 ~ 8, it is characterised in that it is prepared
Method comprises the following steps:
Step one, according to above-mentioned formula metering, epoxide, thinner, chelate compound are rendered to explosion-proof high speed successively
Hybrid reactor, mixes 5-8min under the conditions of 55-62 DEG C；
Step 2, throw in the calcium salt main stabilizer of above-mentioned formula metering, zinc salt main stabilizer, brucite the most in order, at 55-
15-20min is mixed under the conditions of 62 DEG C；
Step 3, finally beta-diketon and antioxidant are rendered to high speed reactor, under the conditions of 55-62 DEG C, mix 25-35min
After, then standing froth breaking 10-15min, cooling material, to 35 ± 2 DEG C, i.e. prepares the transparent shape heat stabilizer of paste without phenol.
The preparation method of the transparent shape heat stabilizer of paste without phenol the most according to claim 9, it is characterised in that: described step
Rapid one and the rotating speed of mixed at high speed reactor of step 2 be respectively 600-1200r/min.
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